EP1757990B1 - Harzzusammensetzungen zur Miniaturizierung des Abstands zwischen Harzmustern und Verfahren zu deren Verwendung - Google Patents

Harzzusammensetzungen zur Miniaturizierung des Abstands zwischen Harzmustern und Verfahren zu deren Verwendung Download PDF

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Publication number
EP1757990B1
EP1757990B1 EP05743737.8A EP05743737A EP1757990B1 EP 1757990 B1 EP1757990 B1 EP 1757990B1 EP 05743737 A EP05743737 A EP 05743737A EP 1757990 B1 EP1757990 B1 EP 1757990B1
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resin
group
hydroxyl group
solvent
resin composition
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EP1757990A4 (de
EP1757990A1 (de
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Hirokazu c/o JSR Corporation SAKAKIBARA
Takayoshi c/o JSR Corporation ABE
Takashi c/o JSR Corporation CHIBA
Toru c/o JSR Corporation KIMURA
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JSR Corp
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JSR Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes

Definitions

  • the present invention relates to a resin composition for miniaturizing the resin pattern space or hole used for causing pattern spaces or holes formed by patterning to shrink by a heat treatment and to a method therefore. More specifically, the invention relates to a resin composition for miniaturizing the resin pattern space or hole and to a method therefor which , owing to increased wettability for photoresist patterns due to the use of an alcoholic solvent, can easily cover patterns with a diameter of 100 nm or less with a coating without incorporating bubbles therein and, when applying the resin composition, can be applied using the cup or waste-water-processing facility used for applying the underlayer coating or photoresist without newly introducing an aqueous-type coating cup or waste-water-processing facility.
  • a lithography process for manufacturing semiconductors demands a higher degree of miniaturization according to the progress of downsizing of semiconductor devices.
  • various methods for forming fine patterns using a photoresist material responding to irradiation with rays with a short wavelength such as an ArF excimer laser, F 2 excimer laser, and the like have been studied.
  • a limitation to the degree of miniaturization is unavoidable due to the restriction of wavelength of rays to which the photoresist material is exposed, researches to enable formation of detailed patterns which surpass the wavelength limit have been undertaken heretofore.
  • a method for miniaturizing resist patterns by a process comprising patterning a resist for electron beams such as polymethyl methacrylate, applying a positive-tone resist onto the resist pattern, treating the positive-tone resist with heat to form a reaction layer on the boundary of the resist pattern and the positive resist layer, and removing the unreacted part of the positive-tone resist (Patent Document 1), a method of forming a reaction layer between a lower layer resist pattern and an upper layer resist using heat crosslinking with an acid generator or an acid (Patent Document 2), a method for manufacturing a semiconductor device using a fine pattern-forming material comprising a water soluble resin, a water-soluble crosslinking agent, or a mixture of these dissolved in an aqueous solvent, but not containing a photosensitive component, as a solution for applying an upper layer resist (Patent Document 3), a method comprising forming a photosensitive layer of a chemically-amplified resist on a substrate, irradiating to form an image and developing to
  • a fine pattern-forming material using the above-mentioned water-soluble resin has a problem of low resistance to dry etching due to a limitation of water solubility. Low dry etching resistance leads to a problem of inaccurate transcription of a resist pattern to a substrate when a pattern is transferred to the substrate by dry etching using the resist pattern as a mask in fabricating a semiconductor device.
  • Patent Documents 5 and 6 a heat flow process which comprises forming a photoresist pattern on a substrate, heating or radiating the pattern to fluidize the photoresist pattern, and reducing the pattern size to a size smaller than the resolution limit has been proposed.
  • the coating agent for miniaturizing a resist pattern is an aqueous-type agent and can only insufficiently cover fine resist patterns such as contact holes with a diameter of 100 nm or less.
  • a cup required for exclusively applying the aqueous-type agent results in a cost increase.
  • the coating agent has a problem of freezing or depositing at a low temperature during transportation and the like.
  • US2003/0143490A1 discloses a resist pattern thickness reducing material having at least one type selected from a water soluble resin and an alkali soluble resin.
  • An object of the present invention is to provide a resin composition which, in in miniaturizing the resin pattern spaces or holes by a heat treatment of a resist pattern formed by using a photoresist, can be applied onto the resist pattern, can cause the resist pattern spaces or holes to smoothly shrink by heat treatment, and can be easily washed away by a treatment with an alkaline aqueous solution, and a method for efficiently miniaturizing the resin pattern spaces or holes using the resin composition. This is achieved by the subject-matter of the independent claims.
  • the resin composition as defined in claims 1 and 2 of the present invention comprises a resin containing a hydroxyl group, a crosslinking component, and a solvent and can miniaturize pattern spaces or holes formed by a resist material, wherein the solvent dissolves the resin and the crosslinking component, but cannot dissolve the resist material.
  • the solvent includes an alcohol selected from 1-butanol, 2-butanol, and 4-methyl-2-pentanol.
  • the solvent including the alcohol contains not more than 10 wt% of water for the total solvent.
  • the hydroxyl group (-OH) contained in the resin is at least one hydroxyl group selected from hydroxyl groups originating from an alcohol, a phenol, or a carboxylic acid.
  • the crosslinking component can comprise at least one compound selected from the group consisting of a compound having the group shown by the following formula (1) and a compound containing two or more cyclic ether as reactive groups, wherein R 1 and R 2 individually represent a hydrogen atom or a group shown by the following formula (2), provided that at least one of R 1 and R 2 is the group shown by the following formula (2), wherein R 3 and R 4 individually represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 1 to 6 carbon atoms, or R 3 and R 4 bond together to form a ring having 2 to 10 carbon atoms, and R 5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the method of the present invention comprises a step of forming a resist pattern on a substrate, a step of forming a coating of the resin composition of the present invention on the resist pattern, a step of treating the coated substrate with heat to cause a crosslinking of the resin composition, and a step of removing the coating film of the non-crosslinked resin composition with an alkaline aqueous solution and washing the substrate with water.
  • the resin composition of the present invention excels in applicability to fine resist patterns and controllability of the size of cured film due to inclusion of hydroxyl group-containing resin, a crosslinking component, and a solvent that can dissolve the resin and the crosslinking component, but cannot dissolve the resist material. For this reason, the resist pattern space can be effectually and accurately miniaturized and patterns surpassing the wavelength limit can be economically formed at a low cost with minimal pattern defects regardless of the state of a substrate surface.
  • the resin used in the composition of the present invention exhibits a large shrinkage, only a low temperature dependency during shrinkage, excellent shape retainability after shrinkage, and low pitch dependability. Therefore, the resin composition has a wide process window (or an exposure depth-window) which is a pattern-forming margin to process fluctuation. Moreover, the composition excels in etching resistance.
  • the fine resist pattern formed in this manner is used as a mask for dry etching, trench patterns and holes can be formed with sufficient accuracy on a semiconductor substrate, and semiconductor devices and the like with fine trench patterns and holes can be easily manufactured in a sufficient yield.
  • the resin composition of the present invention is a resin solution containing a resin containing a hydroxyl group and a crosslinking component in an alcoholic solvent.
  • the resin containing a hydroxyl group may be any resin containing a structural unit which has at least one hydroxyl group (-OH) selected from hydroxyl groups originating from an alcohol, a phenol, or a carboxylic acid.
  • a resin a (meth)acrylic resin, a vinyl resin (the (meth)acrylic resin and vinyl resin are hereinafter referred to as "Copolymer I"), a novolak resin, or a mixture of these resins can be used.
  • the resin composition exhibiting excellent etching resistance can be obtained by using the alcohol-soluble resin containing a hydroxyl group.
  • Copolymer I can be obtained by copolymerizing monomers having at least one hydroxyl group selected from an alcoholic hydroxyl group, a hydroxyl group originating from a carboxylic acid, and a phenolic hydroxyl group.
  • monomers having at least one hydroxyl group selected from an alcoholic hydroxyl group, a hydroxyl group originating from a carboxylic acid, and a phenolic hydroxyl group As examples of the monomer containing an alcoholic hydroxyl group, hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, glycerol monomethacrylate, and the like can be given. Of these, preferable monomers are 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. These monomers may be used either individually or in
  • Monomers having a fluoroalkyl group at the ⁇ -position relative to the hydroxyl group shown by the following formula (3) can also be used as a hydroxyl group-containing monomer, wherein R 6 represents a hydrogen atom or a methyl group. R 7 represents a linear or cyclic divalent hydrocarbon group.
  • saturated linear hydrocarbon groups such as a methylene group, ethylene group, propylene group (1,3-propylene group, 1,2- propylene group), tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, hexadecamethylene group, heptadecamethylene group, octadecamethylene group, nonadecamethylene group, icosa methylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 1-methyl-1,4-butylene group, 2-methyl-1,4-butylene group, monocyclic hydrocarbon groups such as cycloalkylene groups having 3 to 10 carbon atoms such as cyclobutylene groups (
  • cyclopentylene groups e.g. a 1,3-cyclopentylene group
  • cyclohexylene groups e.g. a 1,4-cyclohexylene group
  • cyclooctylene groups e.g. a 1,5-cyclooctylene group
  • bridged cyclic hydrocarbon groups such as cyclic hydrocarbon groups with a 2 to 4 rings having 4 to 30 carbon atoms such as a norbornylene groups (e.g. 1,4-norbornylene group, 2,5-norbornylene group), and admantylene groups (e.g. 1,5-admantylene group, 2,6-admantylene group); and the like can be given.
  • an alkylene group having 1 to 4 carbon atoms as a spacer between a bis(trifluoromethyl)hydroxymethyl group and R 7 , particularly when the R 7 is an alicyclic hydrocarbon group.
  • monomers having a 2,5-norbornylene group or 1,2-propylene group as R 7 in the formula (3) are preferable.
  • R 7 is an alicyclic hydrocarbon group.
  • monomers having a 2,5-norbornylene group or 1,2-propylene group as R 7 in the formula (3) are preferable.
  • As a preferable monomer represented by the formula (3) 4,4,4-trifluoro-3-hydroxy-1-methyl-3-trifluoromethyl-1-butyl methacrylate can be given.
  • the proportion of these monomers in the total monomers forming the copolymer is usually 5 to 90 mol%, and preferably 10 to 60 mol%.
  • monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, acrylic acid dimer, (meth)acrylic acid derivatives having a carboxyl group such as dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, or itaconic acid; and the like can be given.
  • dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, or itaconic acid
  • the monomer containing a phenolic hydroxyl group examples include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, ⁇ -methyl-p-hydroxystyrene, ⁇ -methyl-m-hydroxystyrene, ⁇ -methyl-o-hydroxystyrene, 2-allylphenol, 4-allylphenol, 2-allyl-6-methylphenol, 2-allyl-6-methoxyphenol, 4-allyl-2-methoxyphenol, 4-allyl-2,6-dimethoxyphenol, 4-allyloxy-2-hydroxybenzophenone, and the like can be given. Of these, p-hydroxystyrene or ⁇ -methyl-p-hydroxystyrene is preferable.
  • a monomer having an amide group in the molecule shown by the following formula (4) can be given, wherein R 8 and R 10 represent a hydrogen atom or methyl group and R 9 represents a linear or cyclic divalent hydrocarbon group, or single bond.
  • R 8 and R 10 represent a hydrogen atom or methyl group
  • R 9 represents a linear or cyclic divalent hydrocarbon group, or single bond.
  • p-hydroxymethacrylanilide is preferable.
  • the proportion of the monomers having a phenolic hydroxyl group shown by the formula (4) in the total monomers forming the copolymer is usually 30 to 95 mol%, and preferably 40 to 90 mol%.
  • a monomer having a functional group convertible into a phenolic hydroxyl group after copolymerization can also be copolymerized.
  • a monomer having a functional group convertible into a phenolic hydroxyl group after copolymerization can also be copolymerized.
  • p-acetoxystyrene, ⁇ -methyl-p-acetoxystyrene, p-benzyloxystyrene, p-tert-butoxystyrene, p-tert-butoxycarbonyloxystyrene, p-tert-butyldimethylsiloxystyrene, and the like can be given.
  • the functional group can be easily converted into a phenolic hydroxyl group by a suitable treatment, for example, hydrolysis using hydrochloric acid or the like.
  • the proportion of the monomers having the functional group before and after conversion into the phenolic hydroxyl group in the total monomers forming the copolymer is usually 5
  • the proportions of the monomers having an alcoholic hydroxyl group, a hydroxyl group originating from carboxylic acid, or a phenolic hydroxyl group in the total monomers forming the copolymer I are respectively in the above-described ranges. If the amount of the structural unit having a hydroxyl group is too small, the number of the sites reactive with the later-described crosslinking component is insufficient for the resist material to cause pattern shrinkage. If the amount is too great, on the other hand, the resist material may swell during development and fill out the patterns. In the case of the monomer having a phenolic hydroxyl group and the monomer having an alcoholic hydroxyl group, for example, the copolymer may consist only of structural units having hydroxyl groups.
  • other monomers may be copolymerized in order to control hydrophilicity and solubility of the resin.
  • the other monomers herein indicate monomers other than the above-described monomers having at least one hydroxyl group selected from an alcoholic hydroxyl group, a hydroxyl group originating from an organic acid such as a carboxylic acid, and a phenolic hydroxyl group.
  • (meth)acrylic acid aryl esters, dicarboxylic acid diesters, nitrile group-containing polymerizable compounds, amide bond-containing polymerizable compounds, vinyl compounds, allyl compounds, chlorine-containing polymerizable compounds, conjugated diolefins, and the like can be given.
  • dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate
  • (meth)acrylic acid aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate
  • aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and p-t-butoxystyrene
  • (meth)acrylates such as t-butyl (meth)acrylate and 4,4,4-trifluoro-3-hydroxy-1-methyl-3-trifluoromethyl-1-butyl (meth)acrylate
  • nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile
  • amide bond-containing polymerizable compounds such as acrylamide and methacrylamide
  • the copolymer I is prepared by, for example, polymerizing the monomers corresponding to each of the above recurring units in an appropriate solvent in the presence of a chain transfer agent, as required, using a radical polymerization initiator such as hydroperoxides, dialkyl peroxides, diacyl peroxides, or azo compounds.
  • a radical polymerization initiator such as hydroperoxides, dialkyl peroxides, diacyl peroxides, or azo compounds.
  • alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane
  • cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, and norbornane
  • aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and cumene
  • halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, and chlorobenzene
  • saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate, methyl propionate, and propylene glycol monomethyl ether acetate
  • the polymerization temperature is usually from 40 to 120°C, and preferably from 50 to 100°C.
  • the reaction time is usually from 1 to 48 hours, and preferably from 1 to 24 hours.
  • the copolymer I have a high purity. Not only is the content of impurities such as halogens or metals preferably small, but also the content of resisual monomers and oligomers is preferably less than the prescribed amount, for example, the content determined by HPLC is preferably 0.1 wt% or less.
  • the copolymer I with a high purity ensures further improvement of process stability, pattern profile, and the like of the resin composition for forming fine patterns of the present invention containing copolymer I and provides a resin composition for forming fine patterns of which the content of foreign matter in a solution and the sensitivity do not change over time.
  • a purification method for the copolymer I obtained in the above method the following methods can be given.
  • a method for removing impurities such as metals a method of causing metals in the polymer solution to be adsorbed using a zeta-potential filter, a method of causing metals to be in a chelate state by washing the polymer solution with an acidic aqueous solution such as oxalic acid or sulfonic acid aqueous solution and removing the metals, and the like can be given.
  • a liquid-liquid extraction method in which the residual monomers and oligomer components are removed by washing with water or a combination of suitable solvents, a purification method in a solution state such as ultrafiltration in which only the monomers and oligomer components having a specific molecular weight or less are extracted and removed, a reprecipitation method in which the residual monomers and the like are removed by adding the polymer solution to a poor solvent dropwise, thereby causing the polymer to coagulate in the poor solvent, a purification method in a solid state in which the resin slurry separated by filtration is washed with a poor solvent, and the like can be given. These methods may be used in combination.
  • the polystyrene-reduced weight average molecular weight Mw of the copolymer I determined by gel permeation chromatography is usually 1,000 to 500,000, preferably 1,000 to 50,000, and particularly preferably 1,000 to 20,000. If the molecular weight is too great, the copolymer may not be removed by a developer after curing with heat; if too small, a uniform coating film may not be formed after application.
  • the novolak resin used in the present invention is preferably soluble in alkali.
  • a novolak resin can be obtained by, for example, addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter referred to as "phenols") and an aldehyde in the presence of an acid catalyst.
  • phenols used in the addition condensation include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, fluoroglycinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, ⁇ -naphthol, ⁇ -naphthol, and the like.
  • the aldehydes include, for example, formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde, and the like.
  • the catalyst for the addition condensation reaction There are no specific limitations to the catalyst for the addition condensation reaction.
  • hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, and the like can be used as the acid catalyst.
  • the weight average molecular weight of the novolac resin is not specifically limited, a preferable range is from 1,000 to 30,000.
  • crosslinking component I a compound having the group shown by the following formula (1)
  • crosslinking component II a compound containing two or more cyclic ethers as reactive groups
  • R 1 and R 2 individually represent a hydrogen atom or a group shown by the following formula (2), provided that at least one of R 1 and R 2 is the group shown by the following formula (2), wherein R 3 and R 4 individually represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 1 to 6 carbon atoms, or R 3 and R 4 bond together to form a ring having 2 to 10 carbon atoms, and R 5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the above-mentioned crosslinking components act as a crosslinking component (curing component) with which the resin containing a hydroxyl group mentioned above reacts and/or the crosslinking components mutually reacts with the action of an acid.
  • the compound (crosslinking component I) shown by the formula (1) is a compound having an imino group, a methylol group, a methoxymethyl group, or the like as a functional group in the molecule, and includes, for example, nitrogen-containing compounds prepared by alkyl-ethrification of all or a part of active methylol group of a compound such as (poly)methylolized melamine, (poly)methylolized glycoluril, (poly)methylolized benzoquanamine, (poly)methylolized urea, and the like.
  • alkyl group a methyl group, ethyl group, butyl group, or a mixture of these groups can be given, and may partly include an oligomer component which is made by condensation.
  • hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, and the like can be given.
  • Cymel 325,Cymel 327, Cymel 703, Cymel 712, Cymel 254, Cymel 253, Cymel 212, Cymel 1128, Cymel 701, Cymel 202, and Cymel 207 which are the compounds of the formula (1) in which either R 1 or R 2 is a hydrogen atom, that is, crosslinking components having an imino group, are preferable.
  • the compound containing two or more cyclic ethers as reactive groups includes, for example, epoxycyclohexyl group-containing compounds such as 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane meta-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexane carboxylate, methylenebis(3,4-epoxycyclohexane), di(3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis(3,4-epoxycyclohexane), di(
  • 1,6-hexanediol diglycidyl ether and dipentaerythritol hexakis(3-ethyl-3-oxetanylmethyl) ether are preferable as the crosslinking component II.
  • the above compounds may be used either individually or in combinations of two or more as the crosslinking component II.
  • the amount of the crosslinking components to be added is 1 to 100 parts by weight, and preferably 5 to 70 parts by weight for 100 parts by weight of the resin having a hydroxyl group. If the amount is less than 1 part by weight, the resin composition cures only inadequately and may not cause pattern shrinkage; if more than 100 parts by weight, there is a possibility that patterns are buried due to excessive curing.
  • the total amount of the resin having a hydroxyl group and crosslinking component in the resin composition including the later-described alcoholic solvent is 0.1 to 30 wt%, and preferably 1 to 20 wt%.
  • the amount of the resin having a hydroxyl group and the crosslinking component is less than 0.1 wt%, the thickness of the coating film is so small that the film may be cut at etched points of the patterns; if more than 30 wt%, the viscosity is too high for the resin to fill out fine patterns.
  • 1-butanol, 2-butanol, and 4-methyl-2-pentanol are used as solvent.
  • These alcoholic solvents may be used either individually or in combinations of two or more.
  • the alcoholic solvents can sufficiently dissolve the resin having a hydroxyl group and the crosslinking component, but cannot dissolve a photoresist film during application to the photoresist film and do not cause intermixing with the photoresist film.
  • solvent refers to the properties of a solvent of being a transparent liquid when a solution in which 10 wt% of the resin having a hydroxyl group and the crosslinking component are dissolved (at 25°C for one hour) is inspected by naked eye observation
  • not dissolve a photoresist film refers to the properties of a solvent of retaining the photoresist film without changing its shape when 10 wt% of the photoresist film is dipped in the solvent (at 25°C for one hour) as inspected by naked eye observation.
  • the alcoholic solvents contain water in an amount of 10 wt% or less, and preferably 1 wt% or less of the total amount of solvents used. If more than 10 wt%, the solubility of the resin having a hydroxyl group decreases. An absolute alcohol solvent which does not contain water is more preferable.
  • another solvent may be mixed in order to adjust applicability.
  • the other solvents allow the resin composition for forming fine patterns to be evenly applied to the photoresist film without eroding the photoresist film.
  • cyclic ethers such as tetrahydrofuran and dioxane
  • alkyl ethers of polyhydric alcohol such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; alkyl ether acetates of polyhydric alcohol such as ethylene glycol ethyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate; aromatic hydrocarbons such as toluene and xylene
  • the amount of the other solvents is 30 wt% or less, and preferably 20 wt% or less of the total amount of the solvents. If more than 30 wt%, the solvent causes problems such as erosion of a photoresist film, intermixing with the resin composition for forming fine patterns, and the like. As a result, the resin composition may fill out the resist patterns. When water is mixed, the amount is not more than 10 wt%.
  • a surfactant can be blended with the resin composition for forming fine patterns of the present invention in order to increase applicability, defoamability, leveling properties, and the like.
  • the surfactant commercially available fluorine-containing surfactants such as BM-1000, BM-1100 (manufactured by BM Chemie), Megafac F142D, F172, F173, F183 (manufactured by Dainippon Ink and Chemicals, Inc.), Fluorad FC-135, FC-170C, FC-430, FC-431 (manufactured by Sumitomo 3M, Ltd.), Surflon S-112, S-113, S-131, S-141, S-145 (manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (manufactured by Toray-Dow Corning Silicone Co., Ltd.), and the like can be given.
  • Miniaturized resin pattern spaces or holes (hereinafter referred to as "formation of fine patterns") can be formed by the following method using the above-mentioned resin composition for forming fine patterns.
  • a reflection preventing film (organic film or inorganic film) is formed on an 8 or 12 inch silicon wafer substrate by a conventionally known method such as spin coating.
  • a photoresist applied by a conventionally known method such as spin coating is Prebaked (PB) at a temperature of about 80 to 140°C for about 60 to 120 seconds, for example.
  • the resist film is exposed to radiation such as ultraviolet rays (e.g. g-line, i-line, etc.), a KrF excimer laser, an ArF excimer laser, X-rays, electron beams, or the like and subjected to post exposure baking (PEB) at about 80 to 140°C, for example, and developed to form a resist pattern.
  • PEB post exposure baking
  • the above-mentioned resin composition for forming fine patterns of the present invention is applied to the substrate on which the above resist patterns are formed by a conventionally known method such as spin coating.
  • the solvent may vaporize to form the film coated by spin coating.
  • coated film is prebaked (PB) at a temperature of about 80 to 110°C for about 60 to 120 seconds, for example, to form a coating film of the resin composition.
  • the substrate on which the resist patterns are coated with the resin composition is then treated with heat.
  • An acid produced from the photoresist diffuses from the interface with the photoresist into the layers of the resin composition by heat treatment and causes a crosslinking reaction with the resin composition to occur.
  • the state of the crosslinking reaction from the interface of the photoresist is determined by the material of resin composition, the type of photoresist used, and the baking temperature and time.
  • the temperature and time of heat treatment is usually about 90 to 160°C for about 60 to 120 seconds.
  • the coating film of the resin composition is developed using an alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH) or the like (for example, about for 60 to 120 seconds) to dissolve and remove the coating film of the non-crosslinked resin composition.
  • TMAH tetramethylammonium hydroxide
  • the substrate is washed with water, whereby hole patterns, ellipse patterns, trench patterns, and the like can be miniaturized.
  • copolymer and 50 g of 10 wt% sulfuric acid aqueous solution were dissolved in 300 g of propylene glycol monomethyl ether and hydrolyzed at 90°C for six hours.
  • the reaction product was purified by precipitation in a large amount of water until the product was neutralized to obtain 65 g of a copolymer of p-hydroxystyrene and styrene (85:15 mol ratio) with an Mw of 5,500 and Mw/Mn of 1.55.
  • This copolymer is indicated as a resin P-1.
  • Mw and Mn of the resin P-1 and other polymers obtained in the following Synthesis Examples were measured by gel permeation chromatography (GPC) using GPC columns (manufactured by Tosoh Corp., G2000H XL ⁇ 2, G3000H XL ⁇ 1, G4000H XL ⁇ 1) under the following conditions. Flow rate: 1.0 ml/minute, eluate: tetrahydrofuran, column temperature: 40°C, standard reference material: monodispersed polystyrene
  • a polymerization reaction was carried out in the same manner as in the Synthesis Example 1 except for changing the amount of styrene to 20 g and the amount of azobisisobutyronitrile to 10 g to obtain 70 g of a copolymer of p-hydroxystyrene and styrene (75:25 mol ratio) with an Mw of 5,200 and Mw/Mn of 1.51.
  • This copolymer is indicated as a resin P-2.
  • the polymerization was carried out in the same manner as in Synthesis Example 1, except for using 20 g of p-methoxystyrene (P-3-2) instead of styrene, followed by hydrolysis with an acid to obtain 78 g of a copolymer of p-hydroxystyrene and p-methoxystyrene (80:20 mol ratio) with an Mw of 5,900 and Mw/Mn of 1.58.
  • This copolymer is indicated as a resin P-3.
  • P-7-1 p-hydroxymethacrylanilide
  • P-7-2 t-butyl methacrylate
  • 9 g of azobisisobutyronitrile, and 5 g of 2,4-diphenyl-4-methyl-1-pentene were dissolved in methanol and reacted under refluxing conditions (63°C) for 8 hours to polymerize monomers.
  • the polymerization product was purified by precipitation from a mixture of methanol and water and a mixture of isopropyl alcohol and heptane to obtain 120 g of a copolymer of p-hydroxymethacrylanilide and t-butyl methacrylate (70:30 mol ratio) with an Mw of 8,500 and Mw/Mn of 2.08.
  • This copolymer is indicated as a resin P-7.
  • the polymerization was carried out in the same manner as Synthesis Example 5, except for using p-hydroxymethacrylanilide (P-8-1) and styrene (P-8-2) as starting materials to obtain a copolymer of p-hydroxymethacrylanilide and syrene (70:30 mol ratio) with an Mw of 5,200 and Mw/Mn of 1.62.
  • This copolymer is indicated as a resin P-8.
  • the polymerization was carried out in the same manner as Synthesis Example 5, except for using p-hydroxymethacrylanilide (P-9-1) and p-t-butoxystyrene (P-9-2) as starting materials to obtain a copolymer of p-hydroxymethacrylanilide and p-t-butoxysyrene (70:30 mol ratio) with an Mw of 7,000 and Mw/Mn of 1.77.
  • This copolymer is indicated as a resin P-9.
  • the polymerization was carried out in the same manner as Synthesis Example 5, except for using p-hydroxymethacrylanilide (P-10-1) and 4,4,4-trifluoro-3-hydroxy-1-methyl-3-trifluoromethyl-1-butyl methacrylate (P-10-2) as starting materials to obtain a copolymer of p-hydroxymethacrylanilide and 4,4,4-trifluoro-3-hydroxy-1-methyl-3-trifluoromethyl-1-butyl methacrylate (85:15 mol ratio) with an Mw of 9,700 and Mw/Mn of 1.99.
  • This copolymer is indicated as a resin P-10.
  • the polymerization was carried out in the same manner as Synthesis Example 5, except for using p-hydroxymethacrylanilide (P-11-1) and 3-tricyclo[4.3.0.1 2,5 ]decane methacrylate (P-11-2) as starting materials to obtain a copolymer of p-hydroxymethacrylanilide and 3-tricyclo[4.3.0.1 2,5 ]decane methacrylate (70:30 mol ratio) with an Mw of 8,000 and Mw/Mn of 1.80. This copolymer is indicated as a resin P-11.
  • the resin compositions for forming fine patterns were obtained by adding the resins containing a hydroxyl group, crosslinking components, alcoholic solvents, and other additives at proportions shown in Table 1, stirring the mixtures using stirring blades for three hours (at 100 rpm), filtering the reaction mixture through a filter with a pore diameter of 100 nm.
  • substrates for evaluation with resist patterns were prepared by the following methods. After forming a coating with a thickness of 77 nm (after prebaking at 205°C for 60 seconds) using an underlayer reflection preventing film ARC29A (manufactured by Brewer Science, Inc.) on an 8-inch silicon wafer by spin coating using Clean Track Act 8 (Tokyo Electron, Ltd.), patterns were produced using JSR ArF AR1244J (an alicyclic radiation sensitive resin composition manufactured by JSR, Corp.).
  • the substrate obtained in this process is indicated as a substrate A for evaluation.
  • a number of substrates A for evaluation were prepared under the same conditions.
  • patterns corresponding to a mask pattern with a hole diameter of 100 nm and a line space of 100 nm bias: + 30 nm, i.e. hole diameter of 130 nm and line space of 70 nm on the mask) were inspected to measure the resist pattern hole diameter using a scanning electron microscope ("S-9360" manufactured by Hitachi High-Tech Fielding Corp.).
  • the substrates for evaluation with resist patterns coated with the resin compositions for forming fine patterns in Examples shown in Table 1 were evaluated as follows. The evaluation results are shown in Table 2.
  • a coating film with a thickness of 300 nm was obtained on the above-mentioned substrate A for evaluation by spin coating the resin compositions for forming fine patterns shown in Table 1 using Clean Track Act 8 and baking (100°C, 90 seconds). Then, 20 points on a cross-section of a 100 nm diameter pattern area were inspected using a scanning electron microscope ("S-4800" manufactured by Hitachi High-Tech Fielding Corp.). Embedding properties were regarded as "Good” if there were no voids such as air bubbles in the pattern, and as "Bad” if voids were observed. In Examples 8 to 23, the films were prepared only by spin coating without baking.
  • a coating film with a thickness of 300 nm obtained by applying the resin compositions for forming fine patterns shown in Table 1 to the above-mentioned substrate A for evaluation by spin coating using Clean Track Act 8 and baking at 100°C for 90 seconds was baked under the conditions for the shrink rate evaluation shown in Table 1 in order to cause the resist pattern to react with the resin composition.
  • the substrate was then subjected to paddle development for 60 seconds using a 2.38 wt% of TMAH aqueous solution as a developer jetted from the LD nozzle of the Clean Track Act 8, rinsed with ultrapure water, and spin-dried by swinging at 4,000 rpm for 15 seconds.
  • the substrate obtained in this process is indicated as a substrate B for evaluation.
  • the films were prepared only by spin coating without baking.
  • the substrate was subjected to paddle development using ultrapure water as a developer jetted from LD nozzles of the Clean Track Act 8 for 60 seconds and spin-dried by swinging at 4,000 rpm for 15 seconds.
  • the pattern shrinkage was evaluated to be "Good” when the difference of the angle of the side wall 2 of the hole pattern 2 to the substrate 1 before the pattern shrinkage ( ⁇ ) (see FIG 1(a) ) and after the pattern shrinkage ( ⁇ ') (see FIG 1(b) ) is not more than 3° (see FIG 1 ) and when pattern deterioration t' is seen on the pattern on the substrate B for evaluation only for parts from the substrate 1 exceeding 80 (see FIG 2(b) ), provided that the resist film thickness t in the substrate A for evaluation (see FIG 2(a) ) is regarded as 100, and otherwise evaluated to be "Bad” (see FIG 2 ).
  • the results of evaluation of Comparative Examples 1 to 3 are indicated by asterisks in Table 2, because the evaluation was impossible due to non-uniform embedding conditions and a great shrink rate fluctuation.
  • the pattern defect evaluation was carried out using the products prepared in Examples 9, 12, 13, and 21 and Comparative Example 3. Pattern defects were measured after forming a pattern in the photoresist. After applying the resin composition for forming fine patterns, followed by baking and developing, the defects were measured again using a defect measuring instrument ("Wafer defect inspection instrument 2351" with a UV clear vision field pattern , manufactured by KLA Tencor) under the same conditions. In the measurement, a pattern of 150 nm hole/300 nm pitch was formed on an 8 inch wafer and defects in a measuring area of 37.590 cm 2 were measured. Defects of which the coordinates before and after pattern miniaturization remain the same and defects of which the coordinates before and after pattern miniaturization are not the same were measured. The results were rated as “Good”, if the total number of these defects was not more than 40, and as "Bad", if more than 40.
  • the substrate B for evaluation was dry-etched using a dry-etching apparatus ("Pinnacle 8000" manufactured by PMT, Inc.) using CF 4 as etching gas under the conditions of a gas flow rate of 75 sccm, a pressure of 2.5 mTorr, and an output of 2,500 W to mainly inspect cross-sections of hole patterns and roughness of the hole pattern peripheral by cross-section SEM.
  • a dry-etching apparatus manufactured by PMT, Inc.
  • CF 4 as etching gas under the conditions of a gas flow rate of 75 sccm, a pressure of 2.5 mTorr, and an output of 2,500 W to mainly inspect cross-sections of hole patterns and roughness of the hole pattern peripheral by cross-section SEM.
  • the evaluation criteria the case in which microscopic pits on the section and the surface were distinctly observed was rated as "Bad", and the case in which the number of microscopic pits was comparatively small was rated as "Good”.
  • the resin composition for forming fine patterns of the present invention can effectively and accurately miniaturize resist pattern spaces and can excellently and economically form patterns surpassing a wavelength limit. Therefore, the resin composition can be used very suitably in the field of microfabrication represented by production of integrated circuit elements which are expected to become increasingly miniaturized in the future.

Claims (6)

  1. Harzzusammensetzung zur Miniaturisierung der Harzmusterzwischenräume oder -löcher, die ein Harz, das eine Hydroxylgruppe enthält, eine Quervernetzungskomponente und ein Lösungsmittel umfasst,
    wobei das Harz, das die Hydroxylgruppe enthält, ein Harz ist, das eine Struktureinheit enthält, welche zumindest eine Hydroxylgruppe (-OH) aufweist, die aus Hydroxylgruppen ausgewählt ist, die von einem Alkohol, einem Phenol oder einer Carbonsäure abstammen,
    wobei das Harz, das die Hydroxylgruppe enthält, die von einem Alkohol abstammt, durch Copolymerisieren eines Monomers mit einer Fluoralkylgruppe an einem Kohlenstoffatom in einer α-Position relativ zu der Hydroxylgruppe erhältlich ist, und,
    wobei das Lösungsmittel ein Alkohollösungsmittel ist, das Wasser in einem Gehalt von 10 Gew.-% oder weniger des gesamten Lösungsmittels enthält, wobei das Alkohollösungsmittel einen Alkohol ausgewählt aus 1-Butanol, 2-Butanol und 4-Methyl-2-pentanol enthält.
  2. Harzzusammensetzung zur Miniaturisierung der Harzmusterzwischenräume oder -löcher, die ein Harz, das eine Hydroxylgruppe enthält, eine Quervernetzungskomponente und ein Lösungsmittel umfasst,
    wobei das Harz, das die Hydroxylgruppe enthält, ein Harz ist, das eine Struktureinheit enthält, welche zumindest eine Hydroxylgruppe (-OH) aufweist, die aus Hydroxylgruppen ausgewählt ist, die von einem Alkohol, einem Phenol oder einer Carbonsäure abstammen,
    wobei das Harz, das eine Hydroxylgruppe aufweist, die von einem Phenol abstammt, durch Copolymerisieren eines phenolische-Hydroxylgruppe-enthaltenen Monomers mit einer Amidbindung in dem Molekül erhältlich ist, und,
    wobei das Lösungsmittel ein Alkohollösungsmittel ist, das Wasser in einem Gehalt von 10 Gew.-% oder weniger des gesamten Lösungsmittels enthält, wobei das Alkohollösungsmittel einen Alkohol ausgewählt aus 1-Butanol, 2-Butanol und 4-Methyl-2-pentanol enthält.
  3. Harzzusammensetzung zur Miniaturisierung der Harzmusterzwischenräume oder -löcher, die ein Harz, das eine Hydroxylgruppe enthält, eine Quervernetzungskomponente und ein Lösungsmittel umfasst,
    wobei das Harz, das eine Hydroxylgruppe enthält, ein Harz ist, das durch Copolymerisieren zumindest einer Verbindung erhältlich ist, die aus Hydroxyacrylanilid und Hydroxymethacrylanilid ausgewählt ist,
    wobei das Lösungsmittel ein Alkohollösungsmittel ist, das Wasser in einem Gehalt von 10 Gew.-% oder weniger des gesamten Lösungsmittels enthält, wobei das Alkohollösungsmittel einen Alkohol ausgewählt aus 1-Butanol, 2-Butanol und 4-Methyl-2-pentanol enthält.
  4. Harzzusammensetzung nach einem der Ansprüche 1 bis 3,
    wobei die Quervernetzungskomponente zumindest eine Verbindung ist, die aus Verbindungen, die eine durch die folgende Formel (1) gezeigte Gruppe enthalten, und Verbindungen, die zwei oder mehr zyklische Ether als eine reaktive Gruppe enthalten, ausgewählt ist,
    Figure imgb0018
     wobei R1 und R2 unabhängig ein Wasserstoffatom oder eine durch die folgende Formel (2) gezeigte Gruppe darstellen, vorausgesetzt, dass zumindest eines von R1 und R2 die durch die folgende Formel (2) gezeigte Gruppe ist,
    Figure imgb0019
     wobei R3 und R4 unabhängig ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen oder einer Alkoxyalkylgruppe mit 1 bis 6 Kohlenstoffatomen darstellen oder R3 und R4 binden zusammen, um einen Ring mit 2 bis 10 Kohlenstoffatomen zu bilden, und R5 ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen darstellt.
  5. Harzzusammensetzung nach einem der Ansprüche 1 bis 3, wobei die Quervernetzungskomponente eine Verbindung ist, die eine durch die obige Formel (1) gezeigte Gruppe enthält.
  6. Verfahren zur Miniaturisierung der Harzmusterzwischenräume oder -löcher, das einen Schritt des Bildens eines Resistmusters auf einem Substrat, einen Schritt des Bildens einer Beschichtung aus einer Harzzusammensetzung zum Bilden von Feinmustern auf dem Resistmuster, einen Schritt des Behandelns des beschichteten Substrats mit Wärme, um Quervernetzung der Harzzusammensetzung zu verursachen, und einen Schritt des Entfernens des Beschichtungsfilms der nicht quervernetzten Harzzusammensetzung mit einer alkalischen wässrigen Lösung und Waschen des Substrats mit Wasser umfasst, wobei die Harzzusammensetzung die Harzzusammensetzung zur Miniaturisierung der Harzmusterzwischenräume oder -löcher nach einem der Ansprüche 1 bis 3 ist.
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JP3633595B2 (ja) 2001-08-10 2005-03-30 富士通株式会社 レジストパターン膨潤化材料およびそれを用いた微小パターンの形成方法および半導体装置の製造方法
JP3476081B2 (ja) 2001-12-27 2003-12-10 東京応化工業株式会社 パターン微細化用被覆形成剤およびそれを用いた微細パターンの形成方法
JP3953822B2 (ja) * 2002-01-25 2007-08-08 富士通株式会社 レジストパターン薄肉化材料、レジストパターン及びその製造方法、並びに、半導体装置及びその製造方法
US6806026B2 (en) * 2002-05-31 2004-10-19 International Business Machines Corporation Photoresist composition
JP4535066B2 (ja) * 2004-03-24 2010-09-01 Ｊｓｒ株式会社 ポジ型感放射線性樹脂組成物

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JPWO2005116776A1 (ja) 2008-04-03
JP4687651B2 (ja) 2011-05-25
US20070259287A1 (en) 2007-11-08
US8715901B2 (en) 2014-05-06
KR20070022787A (ko) 2007-02-27
KR101129883B1 (ko) 2012-03-28
EP1757990A4 (de) 2011-04-27
WO2005116776A1 (ja) 2005-12-08
EP1757990A1 (de) 2007-02-28
TWI379173B (de) 2012-12-11

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